Vulcanization accelerator



' i so Reissued Aug. 21, 1934 UNITED STATES R; 19,256 PATENT? OFFICE VULCANIZATION ACCELERATOR Ewald Zaucker and Max Biigemann,

Cologne- Mulheim, and Ludwig Orthner, Leverkusen-I.

' G. Werk, Germany, assignors to Aktiengesellschaft,

industrie the-Main, Germany I. G. Farben- Frankfort-on- No Drawing. Original No. 1,942,790, dated January 9, 1934, Serial No. 597,806, March9, 1932. Application for reissue June 20, 1934, Serial No. 731,442. vIn Germany March 11, 1931 18 Claims.

radical C.S.N 1/

C.- I\ wherein a: and y mean vicinal carbon atoms of an aromatic nucleus (benzene or naphthalene nucleus, for example) or :1 means nitrogen and y sulfur, oxygen or the -NH group.

It is the idea of the invention to have found that organic compounds containing the above grouping are valuable vulcanization accelerators,

possessing an especially'good critical temperature,

The new accelerators, furthermore, can .be applied with vulcanization accelerators of other types without the good critical temperature'being substantially impaired.

The following formula: are intended to show some types of compoundspossessing the above allkyl (aryl, aralkyl) 'R. and R1 in the above formula may stand, for example, for similar or dissimilar alkyl, aralkyl or hydroaryl groups or jointly may represent a chain of alkylene groups, which may be interrupted by oxygen or sulfur. The group -etc. Obviously -al1 the compounds in 'question 'mtybvsubstituted-in the mostvariouemanner '-I.-A metal swltflalttli metal mt, ,forwxample) of a compound containing-.the grouping is caused to react with a N halogen amine containing the grouping 1'10 11. A compound containme the grouping is caused to react with a compound containing the grouping is caused to react with a compound cozltainingmo the groupin I at elevated temperature (40-l50 0., for instance). For. egrample:

(The letters a: and y in the.abov:e1 ,groupings are tobe :expla'inedas .mentioned-m,-page 1.)

For mulcanization; purposes the new vulcanization accelenatorsmay be incorporated within rub- 25 ber in any desired manner, for example, by rolling or kneading. lA vulcanizing agent, such as sulfur, selenium, aromatic nitro compounds metal oxides, are added to tthe vulcanization mixture together with or apart from the new,-;, o vulcanization accelerators, and, if desired, filling materials (zinc oxide, carbon black etc.), plasticizing agents (stearie-aciddtam etc.) and other ingredients known to favorably influence vulcanization processes or to: improve the properties 5 of the vulcanization products. vulcanization of the mixture is then performed by heating the same 'to'temperatures usually applied in vulcanization processes (-150 C. for example), until vulcanization is complete.

It may be mentioned that the term rubber as used in the disclosure andin the claims is intended to includenas well natural rubber as the various artificial rubber-like: masses obtainable, for example, by polymerizing butadiene, isoprene, dimethyl-butadienes, chlorobutadiene etc. alone or in admixture with other polymerizable compounds, such asstyrene, vinylnaphthalene, acrylic acid derivatives, unsaturated ketones etc.

The following examples illustrate the invention without restricting it thereto, the parts being by weight:--

Example 1 The reaction products from para-nitrophenyl sulfur chloride and dibutylamine (I), piperidlne (H) sym.-diphenylguanidine (III) and orthotolylbiguanide (IV) were tested under a pressure of 3.5-atmospheres (superatmospheric) in the mixture:- 1

Parts Light crepe 100 Sulfur 3. 5 Zinc oxide 5. 0 Stearic acid 0. 5

' Accelerator 1. 0

In addition the reaction product from N- chloro-piperidine and para-thiokresol (V) was tested under 3.0 atmospheres (superatmospherlc) in the mlxture:--

7 Parts Light crepe 100.0 Sulfur 3.0 Zinc oxide 5.0 Accelerator 1. 0

The following strengths in kg/cm were obtained:

. 1 Tune of heating in 7 minutes I H III IV V Percentage extension 989 933 916 978 over When heated for 60 minutes under atmosphere (superatmospheric) none of the substances specified caused any incipient vulcanization.

Example 2 1.0 part of the reaction product of para-nitrophenylsulfur chloride with dimethylamine (A) 1.0 part of the reaction product of para-nitrophenylsulfur chloride with ethyl cyclohexylamine (B) 0.33'part of dibenzothisizyl-Z-Z'-disulfide+0.67 part of the reaction product of para-nitrophenylsulfur chloride and dibenzylamine (C) 0.33 part of dibenzothiazyl-2.2'-disulflde+0.6'? part of the reaction product of para-nitrophenylsulfur chloride with dicyclohexylamine (D) 0.2 part of dibenzothiazyl-ZQ'-.disulfide+0.3 part of the reaction product of para-nitrophenylsulfur chloride with piperidine+1.0 part of stearic acid (E) 0.1 part of mercaptobenzothiazol+1.0 part of stearic acid+0.4 part of the reaction product of para-nitrophenylsulfur chloride with piperidine (F) were tested in the following vulcanization mixture:

Parts The following strengths in kg/cm were obtained:--

P 2 t h E t of I ressurema mosp ea mg (superat.) (min- A B O D E F utes) Pa oentage extension Similar results are obtained by applying as accelerators the condensation products of orthonitrophenylsulfur-chloride with piperidine or of phenylsulfur chloride-ortho-carboxylic acid with piperidine (in the form of the piperidine salt, melting at152" C.)

v 4 Example 3 {The reaction products of the sodium salt of -mercaptobenzothiazole and N-chloropiperidlne -(A) N-chloromorpholine (B) dimethylchloramine (C) dibutylchloramine (D) were tested in the following mixture:--

The following strengths in kg/cln were obtained:--,,.

1111 Pressure e Tensile strength Percentage extension in atmosheap heres mg super- (min utes) A B o n A B o D Furthermore, the reaction product A was tested "in the following mixtures:--

- Parts Light crepe 100.0 Zinc oxide 5.0 Sulfur 3.0 Stearic acid 1.0

and 0.1 part of reaction product A +0.3 part of diphenylguanidine 0.2 part of reaction product A +0.6 part of dibenzothiazy1-2.2- II I disulfide Time Tensille strength Percentage Pressure in atmosph. of g m glam 'extgnswn (superatm;) g

- utes) I n I II Example! The product of the action of N-chloropiperi'dme on the potassium "salt of 3-phenyl-5-mercaptc- 1.3.4-thindiazole-2-thione was-tested under 3 atmospheres above atmospheric pressure in the miriture:

Parts Light crepe 100.0 Sulfur 3L0 Zinc oxide- 5.0

Accelerator The following results of testing were obtained:-

Percentage "utension Strength Time of heating in minutes. in kg/cm' ."piperidine, phenylsulfurchloride ortho carbox- -ylic-acid +ipiperidine (in form of thezpiperidine salt), 2;4-dinitrophenylsulfurbromide monophenylguanidine, phenylsulfurchloride morpholine, para-tolylsulfurchloride dicyclo'hexylamine, para-tolylsulfurchloride+dimethylamine, para-nitrophenylsulfurchloride diethylamine, ortho carbmethoxy phenylsulfurohloride ethylcyclohexylamine, ortho-nitrophenylsulfurchloride diethanolamine, orthoor :para-nitrophenylsulfurchloride .methyl-benzylamine, orthoor para nitrophenylsulfurchlorlde methyl-'ethylamine, thiocresol N-chloropiperidine, 2 mercapto- 4-phenyl 1.354 thlodi azole-fi-thion N-chloropiperidine, Z-mercaptobenzothiazole N-chloropiperidine, 2mercaptobenzothiazole N-chloromorpholine, 2-mer- '--captobenzothiazole N chlorodimethylamine, 2-mercaptobenzothiazole N chlorodibutyl amine, Z-me'rcaptothiazoline N-chloropiperidine, 2 mercaptoimidazoline .i-chlorodi methylamine, 2 mercapto 4 -phenyl -.1.3.4

' "thiodiazoline N-chlorodibuty amine, 2 -mer-- capto-benzoxazole N-chloropiperidina z-mercaptoberizimidazole N-chloropiperidine, 6-nitro-2-mercaptobenzothiazole N-chloropiperidine, 6 dimethylamino 2 -'mercaptobenzo thiazole N chlorOpiperidine, mercaptobenzometathiazone N-chlorodimethylamine, 2-mercapto-4-phenyl-5-methyl 1.3.4 thiodiazoline N-chloropiperidine.

We claim: 7

1. vulcanization accelerators consisting Joi organic compounds containing the grouping:-

sass/ wherein: andy mean,vicinal carbon atoms of copes an aromatic nucleus, or :n: :means and 1 sulfur, oxygen or the NI-I-group.

2. vulcanization accelerators consisting of compounds of the probable formula:

wherein a means sulfur, oxygen-or the -NH- group, the "bis jointly stand for the group --CH2 CH2- or represent vicinal carbon atoms of an aromatic nucleus, R and R1 stand foralkyl, -aralky1, hydroaryl, or R and R1 jointly stand for an alkylene group, which may'be'interrupted by oxygen or sulfur I3. vulcanization acozzlerators consisting of compounds of -the probable "formula:-

5. vulcanization accelerator consisting --of the compound of the probable formula:-

6. Vulcanizationaccelerator consisting of the compound of the probable formula:-

.zs 'LThe process which comprises incorporating within rubber'a vulcanizing agent and a vulcanization accelerator as claimed in claim 1 and vulcanizing the mixture.

8, The process which comprises incorporating within rubber'sulfur-and a vulcanization accelerator as claimed in claim 2'and vulcanizing the mixture.

9.'The process'which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed'in claim 3 and vulcanizing the mixture.

10. The process which comprises incorporating within rubber sulfur and a vulcanization'accelera- "tor as claimed in claim 'i and vulcanizing the mixture.

11. The process which comprises incorporating within rubber sulfur and a'vulcanization accelerator' as claimedin claim 5 and vulcanizing the mixture.

12. The process which comprises incorporating within rubber sulfur and avulcanizatlon accelerator as claimed .in claim 6 and vulcanizing the 'mixture.

13. A vulcanized rubber derived from natural rubber or an artificial rubber-like mass combined with .a vulcanizing agent and a vulcanization accelerators-claimed in claiml.

14. a vulcanized rubber-derived-irom natural rubber combined with sulfur and a vulcanization accelerator as claimed in claim 5.

18. A vulcanized rubber derived from natural rubber combined with sulfur and a vulcanization accelerator as claimed ,in claim 6'.

EWALD ZA UCKER. LUDWIG OR'I'HNER. MAX BGGEMANN. 

